Olefin polymerization catalyst and polymerization process

ABSTRACT

A polymerization catalyst for the polymerization and copolymerization of olefin monomers and the copolymerization of olefin monomers with other monomers selected from, for example, norbornenes and styrenes are disclosed. The polymerization catalysts disclosed contain a metal center selected from Ti, Zr, Hf, Ni and Pd with at least one chelating ligand.

This application is a continuation of prior U.S. patent application Ser.No. 11/054,631, filed Feb. 9, 2005 now U.S. Pat. No. 7,037,987, whichapplication claims the benefit of U.S. Provisional Application Ser. No.60/556,802, Mar. 26, 2004.

The present invention relates to a polymerization catalyst useful forthe polymerization and copolymerization of olefins. The presentinvention also relates to olefin polymerization and copolymerizationprocesses using such polymerization catalysts.

Polymers and copolymers of olefins generally exhibit excellentmechanical properties suitable for use in many fields of application.These materials have become so widely used it is hard to imagine lifewithout them. Light, waterproof and resistant to corrosion, they arefrequently the designer's first choice for such disparate items such aswater pipes, trash bags, hair combs, fibers for clothing and roadconstruction, automobile body parts, and packaging for food andmedicine.

One class of catalysts for the polymerization and copolymerization ofolefins is disclosed by Matsui et al. in U.S. Pat. No. 6,593,266. Matsuiet al. disclose a catalyst that contains (A) a transition metal compoundrepresented by the general formula (i) and, optionally, (B) at least onecompound selected from an organometallic compound, an organoaluminumoxycompound and a compound that reacts with the transition metalcompound (A) to form an ion pair. Formula (i) is disclosed by Matsui etal. as follows:

wherein M is a transition metal atom selected from Group 3 to Group 11of the periodic table; m is an integer from 1 to 6; A is —O—, —S—, —Se—,or —N(R⁵)—; D is —C(R⁷)(R⁸)—, —Si(R⁹)(R¹⁰)—, or the like; Z is —R¹³ and—R¹⁴, ═C(R¹⁵)R¹⁶, ═NR¹⁷ or the like, R¹ to R¹⁷ are each selected from H,a hydrocarbon group or the like; n is a number satisfying a valence ofM; and X is a halogen, a hydrocarbon group or the like.

Notwithstanding, a need still exists for new olefin polymerizationcatalysts that exhibit high polymerization activity. There also exists aneed for catalysts for the polymerization of ethylene that provides asubstantially linear product (i.e. polyethylene with a lower degree ofbranching). There further exists a need for catalysts that will enablethe preparation of substantially linear polymers while exhibitingtolerance to polar impurities such that they are capable ofcopolymerizing monomers bearing polar substituents. The polymerizationcatalysts of the present invention may satisfy one or more of theseneeds.

In one aspect of the present invention there is provided apolymerization catalyst comprising: a metal center selected fromtitanium (Ti), zirconium (Zr), hafnium (Hf), nickel (Ni) and palladium(Pd) with at least one chelating ligand comprising a carbene with atleast one anionic moiety, wherein the at least one chelating ligand hasa structure selected from formula I to IV

wherein R is any hydrocarbyl group; each R¹ is independently anyhydrocarbyl group; R² is any hydrocarbyl group; and X is selected fromoxygen, nitrogen and sulfur; wherein both the carbene and the anionicmoiety are coordinated to the metal center.

In another aspect of the present invention, there is provided a processfor preparing a homopolymer comprising contacting at least one α-olefinmonomer with a polymerization catalyst in the presence of an aluminumactivator, wherein the polymerization catalyst comprises: a metal centerselected from titanium (Ti), zirconium (Zr) and hafnium (Hf) with twochelating ligands comprising a carbene with at least one anionic moiety,wherein each of the chelating ligands have a structure independentlyselected from formula I to IV; wherein R is any hydrocarbyl group; eachR¹ is independently any hydrocarbyl group; R² is any hydrocarbyl group;and X is selected from oxygen, nitrogen and sulfur; wherein both thecarbene and the anionic moiety are coordinated to the metal center.

In another aspect of the present invention, there is provided a processfor preparing a copolymer comprising contacting at least two differentmonomers selected from α-olefins, norbornenes and styrenes with apolymerization catalyst in the presence of an aluminum activator,wherein the polymerization catalyst comprises: a metal center selectedfrom titanium (Ti), zirconium (Zr) and hafnium (Hf) with two chelatingligands comprising a carbene with at least one anionic moiety, whereineach of the chelating ligands have a structure independently selectedfrom formula I to IV; wherein R is any hydrocarbyl group; each R¹ isindependently any hydrocarbyl group; R² is any hydrocarbyl group; and Xis selected from oxygen, nitrogen and sulfur; wherein both the carbeneand the anionic moiety are coordinated to the metal center.

In another aspect of the present invention, there is provided a processfor preparing a homopolymer comprising contacting ethylene with apolymerization catalyst, optionally in the presence of an aluminumactivator, wherein the polymerization catalyst comprises a metal centerselected from nickel (Ni) and palladium (Pd) with a chelating ligandcomprising a carbene with at least one anionic moiety, wherein thechelating ligand has a structure selected from formula I to IV; whereinR is any hydrocarbyl group; each R¹ is independently any hydrocarbylgroup; R² is any hydrocarbyl group; and X is selected from oxygen,nitrogen and sulfur; wherein both the carbene and the anionic moiety arecoordinated to the metal center.

In another aspect of the present invention, there is provided a processfor preparing a copolymer comprising contacting ethylene, an acrylicmonomer and a polymerization catalyst, optionally in the presence of analuminum activator, wherein the polymerization catalyst comprises ametal center selected from nickel (Ni) and palladium (Pd) with achelating ligand comprising a carbene with at least one anionic moiety,wherein the chelating ligand has a structure selected from formula I toIV; wherein R is any hydrocarbyl group; each R¹ is independently anyhydrocarbyl group; R² is any hydrocarbyl group; and X is selected fromoxygen, nitrogen and sulfur; wherein both the carbene and the anionicmoiety are coordinated to the metal center.

In another aspect of the present invention, there is provided a processfor preparing a copolymer comprising contacting a polymerizationcatalyst with at least two different monomers selected from α-olefins,norbornenes and styrenes in the presence of an aluminum activator,wherein the polymerization catalyst comprises: a metal center selectedfrom titanium (Ti), zirconium (Zr) and hafnium (Hf) with two chelatingligands comprising a carbene with at least one anionic moiety, whereineach of the chelating ligands have a structure independently selectedfrom formula I to IV; wherein R is any hydrocarbyl group; each R¹ isindependently any hydrocarbyl group; R² is any hydrocarbyl group; and Xis selected from oxygen, nitrogen and sulfur; wherein both the carbeneand the anionic moiety are coordinated to the metal center.

In one embodiment of the present invention, the polymerization catalystincludes a metal center selected from titanium (Ti), zirconium (Zr) andhafnium (Hf) with two halide ligands and two chelating ligands; whereinthe two halide ligands are independently selected from chlorine (Cl),bromine (Br) and iodine (I); wherein each chelating ligand comprises acarbene with at least one anionic moiety and wherein each chelatingligand has a structure independently selected from formula I to IV

wherein R may be any hydrocarbyl group, alternatively R may be selectedfrom a hydrocarbon and an aromatic; each R¹ may independently be anyhydrocarbyl group, alternatively each R¹ may independently be selectedfrom hydrogen (H) and methyl (Me), alternatively each R¹ forms part of acyclic aromatic or hydrocarbon group; R² may be any hydrocarbyl group,alternatively R² may be selected from hydrogen (H), methyl (Me),t-butyl, adamantyl, phenyl (Ph) and anthracenyl; and X is selected fromoxygen, nitrogen and sulfur; wherein both the carbene and the anionicmoiety are coordinated to the metal center. In one aspect of thisembodiment, the polymerization catalyst may have a structure selectedfrom formula (V) and (VI)

wherein R, R¹, R², M and X are as defined above for this embodiment andwherein each X¹ is a halide ligand independently selected from whereinthe two halide ligands are independently selected from chlorine (Cl),bromine (Br) and iodine (I).

In another embodiment of the present invention, the polymerizationcatalyst includes a metal center selected from nickel (Ni) and palladium(Pd) with a chelating ligand; wherein the chelating ligand comprises acarbene with at least one anionic moiety and wherein each chelatingligand has a structure independently selected from formula I to IV;wherein R may be any hydrocarbyl group, alternatively R may be selectedfrom a hydrocarbon and an aromatic; each R¹ may independently be anyhydrocarbyl group, alternatively each R¹ may independently be selectedfrom hydrogen (H) and methyl (Me), alternatively each R¹ forms part of acyclic aromatic or hydrocarbon group; R² may be any hydrocarbyl group,alternatively R² may be selected from hydrogen (H), methyl (Me),t-butyl, adamantyl, phenyl and anthracenyl; and X is selected fromoxygen, nitrogen and sulfur; wherein both the carbene and the anionicmoiety are coordinated to the metal center. In one aspect of thisembodiment, the polymerization catalyst further comprises a hydrocarbylligand and a neutral ligand coordinated with the metal center; whereinthe hydrocarbyl ligand is selected from methyl (Me), phenyl (Ph) andmesityl and wherein the neutral ligand is selected from phosphine, amineand pyridine. In another aspect of this embodiment, the polymerizationcatalyst further comprises a chelating hydrocarbyl ligand coordinatedwith the metal center.

The chelating ligands of the present invention comprising a carbene withat least one anionic moiety may be prepared, for example, using thesynthesis method depicted in the following equations:

Chelating hydrocarbyl ligands suitable for use with the presentinvention include allyl, linear and branched C₃–C₂₀ alkenyl, C₆–C₁₅cycloalkenyl, allylic ligands or canonical forms thereof, optionallysubstituted with hydrocarbyl and/or heteroatom substituents selectedfrom linear or branched C₁–C₅ alkyl, linear or branched C₁–C₅ haloalkyl,linear or branched C₂–C₅ alkenyl and haloalkenyl, halogen, sulfur,oxygen, nitrogen, phosphorus, and phenyl optionally substituted withlinear or branched C₁–C₅ alkyl, linear or branched C₁–C₅ haloalkyl, andhalogen; wherein the cycloalkyl and cycloalkenyl groups may bemonocyclic or multicyclic; wherein the aryl groups can be a single ring(e.g., phenyl) or a fused ring system (e.g., naphthyl); wherein thecycloalkyl, cycloalkenyl and aryl groups can be taken together to form afused ring system; and wherein each of the monocyclic, multicyclic andaryl ring systems may optionally be monosubstituted or multisubstitutedwith a substituent independently selected from hydrogen, linear andbranched C₁–C₅ alkyl, linear and branched C₁–C₅ haloalkyl, linear andbranched C₁–C₅ alkoxy, chlorine, fluorine, iodine, bromine, C₅–C₁₀cycloalkyl, C₆–C₁₅ cycloalkenyl and C₆–C₃₀ aryl.

In one aspect, the chelating hydrocarbyl ligand may be selected from thegroup of structures depicted in Structures A–E bound to a metal center Mor a metal center with a ligand M(L).

Monomers suitable for use with the present invention include α-olefins,norbornenes, styrenes and (meth)acrylates.

α-Olefins suitable for use with the present invention include, forexample, ethylene, propylene, 1-butene, 1-hexene and 1-octene.Norbornene-type monomers suitable for use with the present inventioninclude, for example, norbornenes bearing polar groups such ascarboxylic acid ester. The term “norbornene-type monomer” as used hereinand in the appended claims is meant to encompass norbornene, substitutednorbornene, as well as any substituted and unsubstituted higher cyclicderivatives thereof, provided that the subject monomer contains at leastone norbornene-type moiety or substituted norbornene-type moiety.

Norbornene-type monomers suitable for use with the present invention mayinclude substituted norbornene-type monomers and higher cyclicderivatives thereof that contain a pendant hydrocarbyl substituent or apendant functional substituent containing an oxygen atom.

Norbornene-type monomers suitable for use with the present invention mayinclude norbornene-type or polycycloolefin monomers are represented bythe structure below:

wherein W′″ is selected from the group including, but by no meanslimited to, an oxygen, a nitrogen with a hydrogen attached thereto, anitrogen with a linear C₁ to C₁₀ alkyl grouping attached thereto, anitrogen with a branched C₁ to C₁₀ alkyl grouping attached thereto, asulfur and a methylene group of having the formula —(CH₂)n′— wherein n′is an integer from 1 to 5, “a” is a single or a double bond; R³, R⁴, R⁵,and R⁶ each independently represent a hydrogen, a hydrocarbyl or afunctional substituent; m is an integer from 0 to 5, with the provisothat when “a” is a double bond, both (i) one of R³ and R⁴ is not presentand (ii) one of R⁵ and R⁶ is not present.

The term “hydrocarbyl groups” as used herein and in the appended claimsencompasses hydrogen, hydrocarbyl groups, halohydrocarbyl groups,perhalohydrocarbyl groups and perhalocarbyl groups. In one embodiment,R³, R⁴, R⁵ and/or R⁶, may independently represent hydrogen, linear orbranched C₁–C₁₀ alkyl, linear or branched C₂–C₁₀ alkenyl, linear orbranched C₂–C₁₀ alkynyl, C₄–C₁₂ cycloalkyl, C₄–C₁₂ cycloalkenyl, C₆–C₁₂aryl, and C₇–C₂₄ aralkyl. In one embodiment, R³ and R⁴ or R⁵ and R⁶ maycollectively represent a C₁–C₁₀ alkylidenyl group. Representative alkylgroups include, but are by no means limited to, methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl,hexyl, heptyl, octyl, nonyl and decyl. Representative alkenyl groupsinclude, but are by no means limited to, vinyl, allyl, butenyl andcyclohexenyl. Representative alkynyl groups, include but are by no meanslimited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl and 2-butynyl.Representative cycloalkyl groups include, but are by no means limitedto, cyclopentyl, cyclohexyl and cyclooctyl substituents. Representativearyl groups include, but are by no means limited to, phenyl, naphthyland anthracenyl. Representative aralkyl groups include, but are by nomeans limited to, benzyl and phenethyl. Representative alkylidenylgroups include, but are by no means limited to, methylidenyl andethylidenyl groups.

When the pendant group(s) is(are) a functional substituent, R³, R⁴, R⁵may R⁶ independently represent a radical selected from(CH₂)_(n)—CH(CF₃)₂—O—Si(Me)₃, —(CH₂)_(n)—CH(CF₃)₂—O—CH₂—O—CH₃,—(CH₂)_(n)—CH(CF₃)₂—O—C(O)—O—C(CH₃)₃, —(CH₂)_(n)—C(CF₃)₂—OH,—(CH₂)_(n)C(O)NH₂, —(CH₂)_(n)C(O)Cl, —(CH₂)_(n)C(O)OR⁷, —(CH₂)_(n)—OR⁷,—(CH₂)_(n)—OC(O)R⁷, —(CH₂)_(n)—C(O)R⁷, —(CH₂)_(n)—OC(O)OR⁷,—(CH₂)_(n)Si(R⁷)₃, —(CH₂)_(n)Si(OR⁷)₃, —(CH₂)_(n)—O—Si(R⁷)₃ and—(CH₂)_(n)C(O)OR⁸ wherein n independently represents an integer from 0to 10 and R⁷ independently represents hydrogen, linear or branchedC₁–C₂₀ alkyl, linear or branched C₁–C₂₀ halogenated or perhalogenatedalkyl, linear or branched C₂–C₁₀ alkenyl, linear or branched C₂–C₁₀alkynyl, C₅–C₁₂ cycloalkyl, C₆–C₁₄ aryl, C₆–C₁₄ halogenated orperhalogenated aryl, and C₇–C₂₄ aralkyl. Representative hydrocarbylgroups set forth under the definition of R⁷ are the same as thoseidentified above under the definition of R³ to R⁵. As set forth aboveunder R³ to R⁶ the hydrocarbyl groups defined under R⁷ may behalogenated and perhalogenated. Aluminum activators suitable for usewith the present invention include, for example, methaluminoxane,isobutylaluminoxanes, hydroxyisobutylaluminoxane,hydrocarbylhaloaluminoxanes such as those described in WO 2003082466 andionic aluminoxanates such as those described in WO 2003082879.

Some embodiments of the present invention will now be described indetail in the following Examples.

EXAMPLE 1 Synthesis of N-(mesityl)-oxanilic acid ethyl ester

2,4,6-Trimethylaniline (20 ml, 142 mmol, 1.0 equiv) and triethylamine(20 ml, 143 mmol, 1 equiv) were dissolved in dry tetrahydrofuran (“THF”)(150 ml), forming a solution. The solution was cooled to 0° C., andethyl chlorooxoactetate (15.3 ml, 142 mmol, 1.0 equiv) was added slowlyvia syringe. Precipitation of a white solid occurred immediately uponaddition of the ethyl chlorooxoacetate. The solution was allowed to stirovernight, warming to room temperature. The solid was then filtered off,and the organic layer was washed with 2 M HCl solution (2×100 ml). Theaqueous layer was washed with ethyl acetate, and the combined organiclayers were washed with brine (100 ml), and dried over MgSO₄. Thesolvent was then removed under reduced pressure, leaving a yellowishsolid. The yellowish solid was recrystallized from hexanes/EtOAc (9:1),producing a product, white crystalline solid (30.15 g, 128 mmol, 90%yield). ¹H NMR (300 MHz, CDCl₃) δ 8.34 (s, 1H), 6.92 (s, 2H), 4.43 (q,J=7.2 Hz, 2H), 2.28 (s, 3H), 2.20 (s, 6H), 1.45 (t, J=7.2 Hz, 3H); ¹³CNMR (75 MHz, CDCl₃) δ161.2, 154.9, 138.0, 134.9, 129.7, 129.3, 63.8,21.2, 18.6, 14.3. Anal. Calcd for C₁₃H₁₇NO₃: C, 66.36; H, 7.28; N, 5.95.Found: C, 66.56; H, 7.15; N, 6.04.

EXAMPLE 2 Synthesis of N-(2,6-diisopropylphenyl)-oxanilic acid ethylester

2,6-Diisopropylaniline (90%) (10 ml, 48 mmol, 1.1 equiv) andtriethylamine (7.3 ml, 48 mmol, 1 equiv) were dissolved in dry THF (150ml), forming a solution. The solution was then cooled to 0° C., andethyl chlorooxoactetate (5.12 ml, 48 mmol, 1.0 equiv) was added slowlyvia syringe. Precipitation of a white solid occurred immediately uponaddition of the ethyl chlorooxoacetate. The solution was allowed to stirovernight, warming to room temperature. The solid was then filtered off,and the organic layer was washed with 2 M HCl solution (2×100 ml). Theaqueous layer was washed with ethyl acetate, and the combined organiclayers were washed with brine (100 ml), and dried over MgSO₄. Thesolvent was then removed under reduced pressure, leaving a yellowishsolid. The yellowish solid was then recrystallized from hexanes/EtOAc(9:1), producing a product, white crystalline solid (12.15 g, 44 mmol,92% yield). ¹H NMR (300 MHz, CDCl₃) δ 8.36 (s, 1H), 7.34 (t, J=7.1 Hz,1H), 7.20 (d, J=7.8 Hz, 2H), 4.45 (q, J=7.2 Hz, 2H), 3.01 (septet, J=7.2Hz, 2H), 1.47 (t, J=7.2 Hz, 3H), 1.21 (d, J=6.6 Hz, 12H); ¹³C NMR (75MHz, CDCl₃) δ 161.3, 156.1, 146.1, 129.6, 129.2, 124.0, 63.9, 29.1,23.9, 14.2. Anal. Calcd for C₁₆H₂₃NO₃: C, 69.29; H, 8.36; N, 5.05.Found: C, 69.31; H, 8.13; N, 5.10.

EXAMPLE 3 Synthesis of N-(mesityl)-N′-(2-hydroxyphenyl)-oxalamide

N-(Mesityl)-oxanilic acid ethyl ester (5.23 g, 24.4 mmol, 1 eq) and2-aminophenol (2.67 g, 24.4 mmol, 1.0 eq) were dissolved in toluene (50ml), forming a suspension. To this suspension was added triethylamine(6.8 ml, 50 mmol, 2 eq). The suspension was then heated to reflux,causing the solids to dissolve. After heating at reflux overnight, theproduct precipitated. At this point, ethyl acetate was added until theprecipitate redissolved. The solution was then washed with 2 M HClsolution (2×100 ml). The aqueous layer was then washed with ethylacetate, and the combined organic layers were washed with brine (100ml), and dried over MgSO₄. The solvent was then removed under reducedpressure, leaving a yellowish solid. The yellowish solid was thenrecrystallized from toluene, producing a product, white crystallinesolid (5.26 g, 17.7 mmol, 72.4% yield). ¹H NMR (300 MHz, CDCl₃) δ 9.69(s, 1H), 8.84 (s, 1H), 8.11 (s, J=7.7 Hz, 1H), 7.51 (dd, J=8.0, 1.8 Hz,1H), 7.14 (ddd, J=1.5, 8.1, 7.2 Hz, 1H), 6.92 (m, 3H), 2.30 (s, 3H),2.22 (s, 6H); ¹³C NMR (75 MHz, CDCl₃) δ 158.2, 157.9, 148.2, 138.2,134.9, 129.5, 129.4, 127.7, 124.3, 122.2, 121.1, 118.9, 21.2, 18.6.Anal. Calcd for C₁₇H₁₈N₂O₃: C, 68.44; H, 6.08; N, 9.39. Found: C, 68.50;H, 5.96; N, 9.44.

EXAMPLE 4 Synthesis ofN-(2,6-diisopropylphenyl)-N′-(2-hydroxyphenyl)-oxalamide

N-(2,6-Diisopropylphenyl)-oxanilic acid ethyl ester (2.78 g, 10 mmol, 1eq) and 2-aminophenol (1.31 g, 12 mmol, 1.2 eq) were dissolved intoluene (50 ml), forming a suspension. To this suspension was addedtriethylamine (2.78 ml, 20 mmol, 2 eq). The suspension was then heatedto reflux, causing the solids to dissolve. After heating at refluxovernight, the product precipitated. At this point, ethyl acetate wasadded until the precipitate redissolved. The solution was then washedwith 2 M HCl solution (2×100 ml). The aqueous layer was then washed withethyl acetate, and the combined organic layers were washed with brine(100 ml), and dried over MgSO₄. The solvent was then removed underreduced pressure, leaving a yellowish solid. The yellowish solid wasthen recrystallized from toluene, producing a product, white crystallinesolid (2.9 g, 8.5 mmol, 85% yield). ¹H NMR (300 MHz, CDCl₃) δ 9.67 (s,1H), 8.84 (s, 1H), 8.12 (s, 1H), 7.50 (dd, J=8.25, 1.8 Hz 1H), 7.37 (t,J=7.2 Hz, 1H), 7.23 (d, J=7.5 Hz, 1H), 7.16 (dt, J=7.7, 1.5 Hz, 1H),6.95 (comp m, 2H), 3.03 (septet, J=6.6 Hz, 2H), 1.22 (d, J=6.9, 12H); ³CNMR (75 MHz, CDCl₃) δ 158.9, 158.2, 148.2, 146.1, 129.4, 127.9, 124.2,124.0, 122.3, 121.2, 119.1, 29.2, 23.9. Anal. Calcd for C₂₀H₂₄N₂O₃: C,70.56; H, 7.11; N, 8.23; O, 14.10. Found: C, 34.90; H, 4.64; N, 5.79.

EXAMPLE 5 Synthesis of N-(mesityl)-oxanilic acid

N-(Mesityl)-oxanilic acid ethyl ester (1.99 g, 8.5 mmol) was dissolvedin THF (50 ml), forming a solution. To this solution was added 1M NaOHsolution (40 ml), and the mixture was then stirred for 2 hours. Diethylether (25 ml) was then added, and the layers were separated. The organiclayer was washed with 1M NaOH solution (40 ml). The aqueous layer wasthen acidified with 2M HCl until precipitation occurred. The precipitatewas then extracted with ethyl acetate (2×50 ml). The ethyl acetate waswashed with brine (50 ml), and then dried over MgSO₄. Removal of thesolvent under reduced pressure provided the product as a white solid(1.74 g, 8.4 mmol, 99% yield). ¹H NMR (300 MHz, CDCl₃) δ 8.51 (s, 1H),6.93 (s, 2H), 2.29 (s,3H), 2.19 (s, 6H); ¹³C NMR (75 MHz, CDCl₃) δ160.0, 156.1, 138.6, 134.7, 129.5, 128.9, 21.2, 18.5. Anal. Calcd forC₁₁H₁₃NO₃: C, 63.76; H, 6.32; N, 6.76. Found: C, 63.59; H, 6.32; N,6.79.

EXAMPLE 6 Synthesis of 2-Amino-4-methyl-6-tert-butylphenol

2-tert-Butyl-4-methylphenol (20.04 g, 122 mmol, 1.0 eq) is dissolved inAcOH (200 ml) and cooled to 0° C. A solution of concentrated nitric acid(7.73 ml, 122 mmol, 1 eq) in an equal volume of acetic acid was thenadded to the solution. Upon addition of the nitric acid, the solutionturned yellow. After addition was complete, the solution was allowed tostir at 0° C. for 2.5 hours until some needles of product were observedto start growing. Deionized water (˜25 ml) was then added, causing agreat deal of precipitation. This was filtered, and water was againadded to the filtrate, causing more precipitate that was again filtered.More precipitation/filtration cycles did not yield substantial furtherproduct. The orange/yellow solid obtained from the filtrations (13.06 g,62.4 mmol, 51% yield) was dried overnight by vacuum. ¹H NMR (300 MHz,CDCl₃) δ 11.40 (s, 1H), 7.77 (d, J=1.5 Hz, 1H), 7.37 (d, J=2.1 Hz, 1H),2.31 (s, 3H), 1.42 (s, 9H); ³C NMR (75 MHz, CDCl₃) δ 153.3, 140.4,136.3, 128.8, 122.5, 35.7, 29.6, 20.0. Anal. Calcd for C₁₁H₁₅NO₃: C,63.14; H, 7.23; N, 6.69. Found: C, 64.52; H, 7.69; N, 5.89. A sample ofthis material, 2-amino-4-methyl-6-tert-butylphenol (4.13 g, 20 mmol, 1.0eq), was then added to an oven dried, two-necked flask, and Pd (10% oncharcoal) (1.051 g, 1 mmol Pd, 0.05 eq) was added. The flask wasevacuated, and filled with argon, and then dry, degassed methanol (50ml) was added. A balloon of hydrogen gas was placed over the reaction,and which was then allowed to stir for 16 hours. The solution was thenfiltered through celite, removing the Pd. The product was stable ininert atmosphere, but was observed to rapidly oxidize when in solution,exposed to air. The clear Pd/C suspension was observed to rapidly turnto a red solution upon filtration on the benchtop. The methanol wasevaporated under reduced pressure, leaving a dark red solid. This darkred solid was then recrystallized from hexane to yield a whitish solid(2.41 g, 13.4 mmol, 68% yield) that was observed to slowly turn redwhile in the solid state. ¹H NMR (300 MHz, CDCl₃) δ 6.67 (d, J=1.5 Hz,1H), 6.61 (d, J=1.8 Hz, 1H), 5.57 (bs, 1H), 3.20 (bs, 2H), 2.22 (s, 3H),1.40 (s, 9H); ¹³C NMR (75 MHz, CDCl₃) δ 144.1, 135.5, 133.4, 129.3,120.7, 119.2, 34.6, 30.0, 21.2.

EXAMPLE 7 Synthesis ofN-(mesityl)-N′-(2-hydroxy-3-tert-butyl-5-methylphenyl)-oxalamide

N-(Mesityl)-oxanilic acid (2.15 g, 10.4 mmol, 1.0 eq), preparedaccording to the synthesis method described in Example 5, and1-hydroxybenzotriazole (2.39 g, 15.6 mmol, 1.5 eq) were added to an ovendried, two-necked flask, forming a solution. THF (100 ml) was then addedand the solution was cooled to 0° C. 1,3-dicyclohexylcarbodiimide (1 Min CH₂Cl₂) (12.5 ml, 12.5 mmol, 1.2 eq) was then added to the solution.The solution was then allowed to stir at 0° for one hour. During thistime, a white precipitate formed. 2-amino-4-methyl-6-tert-butylphenol(1.863 g, 10.4 mmol, 1.0 eq), prepared according to the synthesis methoddescribed in Example 6, was then added to the suspension. The suspensionwas then allowed to stir overnight. The next day, the solvent wasremoved under reduced pressure, and ethyl acetate was added. Theresulting suspension was then filtered to remove the solid. The filtratewas washed with 10% citric acid solution (2×50 ml), 5% NaHCO₃ (2×50 ml)and brine (50 ml). It was dried over MgSO₄, and the solvent was removedunder reduced pressure, leaving a solid which was recrystallized fromhexane to give the product as a white solid (2.92 g, 7.9 mmol, 76%yield). ¹H NMR (300 MHz, CDCl₃) δ 9.55 (s, 1H), 8.77 (s, 1H), 7.84 (s,1H), 7.05 (d, J=1.8 Hz, 1H), 6.92 (m, 3H), 2.30 (s, 3H), 2.28 (s, 3H),2.22 (s, 6H), 1.45 (s, 9H); ¹³C NMR (75 MHz, CDCl₃) δ 158.5, 157.4,146.2, 140.6, 138.1, 134.9, 129.9, 129.6, 129.4, 126.9, 124.9, 121.4,35.3, 30.0, 21.2, 21.0, 18.5. Anal. Calcd for C₂₂H₂₈N₂O₃: C, 71.71; H,7.66; N, 7.60. Found: C, 72.01; H, 8.03; N, 7.36.

EXAMPLE 8 Synthesis ofN-(2,6-diisopropylphenyl)-N′-(2-hydroxy-5-methylphenyl)-oxalamide

N-(2,6-Diisopropylphenyl)-oxanilic acid ethyl ester (5.14 g, 18.5 mmol,1.0 eq) and 2-amino-5-methylphenol (2.28 g, 18.5 mmol, 1 eq) weredissolved in toluene (50 ml), forming a suspension. To this suspensionwas then added triethylamine (2.6 ml, 18.5 mmol, 1 eq). The suspensionwas then heated to reflux, causing the solids to dissolve. After heatingat reflux overnight, the product precipitated. At this point, ethylacetate was added until the precipitate redissolved. The solution wasthen washed with 2 M HCl solution (2×100 ml). The aqueous layer was thenwashed with ethyl acetate, and the combined organic layers were washedwith brine (100 ml), and dried over MgSO₄. The solvent was then removedunder reduced pressure, leaving a yellowish solid. The yellowish solidwas then recrystallized from toluene, producing a product, whitecrystalline solid (5.90 g, 16.6 mmol, 90% yield). ¹H NMR (300 MHz,CDCl₃) δ 9.58 (s, 1H), 8.81 (s, 1H), 7.92 (s, 1H), 7.37 (t, J=7.8 Hz1H), 7.27 (d, J=0.9 Hz, 1H), 7.23 (d, J=7.8 Hz, 2H), 6.97 (dd, J=8.1,2.1 Hz, 1H), 6.90 (d, J=8.1 Hz, 1H), 3.02 (septet, J=6.6, 2H), 2.29 (s,3H), 1.22 (d, J=7.2, 12H); ¹³C NMR (75 MHz, CDCl₃) δ 158.8, 158.2,146.0, 130.7, 129.4, 128.7, 124.0, 123.8, 122.6, 119.1, 29.2, 23.9,20.7. Anal. Calcd for C₂₁H₂₆N₂O₃: C, 71.16; H, 7.39; N, 7.90. Found: C,70.85; H, 7.68; N, 7.73.

EXAMPLE 9 Synthesis ofN-(2,6-diisopropylphenyl)-N′-(2-hydroxy-3-(adamant-1-yl)-5-methylphenyl)-oxalamide

N-(2,6-Diisopropylphenyl)-N′-(2-hydroxy-5-methylphenyl)-oxalamide (5.59g, 15.5 mmol, 1.0 eq), prepared according to the synthesis methoddescribed in Example 8, and 1-adamantol (2.83 g, 18.6 mmol, 1.2 eq) weredissolved in CH₂Cl₂ (150 ml), forming a suspension. To this suspensionwas then added concentrated H₂SO₄ (1 ml). After addition of the acid,the solids eventually went into solution. After stirring at roomtemperature for 24 hours, the TLC (9:1 hexanes:ethyl acetate, visualizedby UV) showed that most of the starting material had gone to product. Atthis point, the solvent was removed under reduced pressure, and theresulting solids were redissolved in ethyl acetate (100 ml). Theresulting solution was then washed with saturated NaHCO₃ (3×50 ml, gasis evolved), and brine, then dried over MgSO₄. The solvent was removedunder reduced pressure, and the resulting solid was purified via columnchromatography to give a product, light yellow solid (3.68 g, 7.5 mmol,48%). ¹H NMR (300 MHz, CDCl₃) δ 9.51 (s, 1H), 8.77 (s, 1H), 7.84 (s,1H), 7.37 (t, J=7.2 Hz 1H), 7.23 (d, J=7.5 Hz, 2H), 7.00 (d, J=2.1 Hz,1H), 6.94 (d, J=1.8 Hz, 1H), 3.01 (septet, J=6.9, 2H), 2.29 (s, 3H),2.18 (bs, 6H), 2.10 (bs, 3H), 1.80 (bs, 6H), 1.22 (d, J=6.9, 12H); ¹³CNMR (75 MHz, CDCl₃) δ 158.3, 158.2, 146.2, 145.8, 140.6, 129.9, 129.2,129.2, 126.8, 124.7, 123.8, 120.9, 40.7, 37.3, 37.1, 29.1, 29.0, 23.6,20.8. Anal. Calcd for C₃₁H₄₀N₂O₃: C, 76.19; H, 8.25; N, 5.73. Found: C,75.89; H, 8.42; N, 5.37.

EXAMPLE 10 Synthesis ofN-(mesityl)-3-(2-hydroxyphenyl)-4,5-dihydro-imidazolium chloride

N-(Mesityl)-N′-(2-hydroxyphenyl)-oxalamide (1.47 g, 4.9 mmol, 1 eq),prepared according to the synthesis method described in Example 3, wasweighed into an oven-dried round-bottom flask. To this was added BH₃-THF(1M in THF) (39 ml, 39.2 mmol, 8 eq). A great deal of bubbling resulted,as the solution turned bright orange. The solution was allowed to refluxovernight. The next day, the solution was observed to have turned clear.The solution was then allowed to cool to room temperature. Methanol wasthen very slowly added to the solution until all bubbling ceased.Concentrated HCl solution (1.5 ml) was then added, and the solvent wasremoved under reduced pressure. The resulting solid was dissolved inmethanol, and then the solvent was again removed under reduced pressure.This process was repeated twice more. In this way, the remaining boronwas removed as B(OMe)₃. Triethylorthoformate (15 ml) was then added tothe resulting solid, forming a suspension. The suspension was thenheated to 100° C. As the suspension was heated, the solid was observedto slowly go into solution. After aproximately one minute at hightemperature, a white solid precipitated. It was allowed to stir for fivemore minutes, and was then filtered. The resulting solid was washed withether, to provide the desired product as a white powder (0.854 g, 2.7mmol, 55% yield). ¹H NMR (300 MHz, CDCl₃) δ 11.43 (s, 1H), 8.84 (s, 1H),7.54 (dd, J=8.25, 1.2 Hz, 1H), 7.05 (dd, J=8.0, 1.2 Hz, 1H), 6.92 (m,2H), 6.73 (dt, J=7.7, 0.9 Hz 1H), 4.80 (t, J=11.4 Hz, 2H), 4.37 (t,J=11.7 Hz, 2H), 2.33 (s, 3H), 2.29 (s, 6H); ¹³C NMR (75 MHz, CDCl₃) δ157.4, 150.0, 141.0, 135.3, 130.7, 130.3, 128.8, 122.8, 120.4, 119.9,118.8, 51.0, 50.4, 21.3, 18.2. Anal. Calcd for C₁₈H₂₁ClN₂O: C, 68.24; H,6.68; N, 8.84. Found: C, 67.86; H, 6.92; N, 8.52.

EXAMPLE 11 Synthesis of1-(2,6-diisopropylphenyl)-3-(2-hydroxyphenyl)-4,5-dihydro-imidazoliumchloride

N-(2,6-Diisopropylphenyl)-N′-(2-hydroxyphenyl)-oxalamide (0.7356 g, 2.2mmol, 1 eq), prepared according to the synthesis method described inExample 4, was treated in a fashion similar to that described in Example10 for N-(mesityl)-N′-(2-hydroxyphenyl)-oxalamide). The resulting solidwas washed with ether, to provide the desired product as a white powder(0.657 g, 1.83 mmol, 85% yield). ¹H NMR (300 MHz, CDCl₃) δ 9.04 (s, 1H),7.57 (dd, J=8.9, 1.2 Hz, 1H), 7.44 (t, J=7.8 Hz, 1H), 7.22 (d, J=7.8 Hz,2H), 7.15 (d, J=6.6 Hz, 1H), 6.97 (dt, J=7.8, 1.8 Hz, 1H), 6.78 (dt,J=8.3, 0.9 Hz, 1H), 4.88 (t, J=11.4 Hz, 2H), 4.44 (t, J=11.1, 2H), 2.95(septet, J=6.6 Hz, 2H), 1.25 (d, J=7.2 Hz, 6H), 1.16 (d, J=6.6 Hz, 6H);¹³C NMR (75 MHz, CDCl₃) δ 157.0, 149.8, 146.6, 131.6, 130.0, 128.7,125.1, 122.6, 120.3, 120.0, 118.6, 52.7, 51.1, 28.9, 25.0, 24.3. Anal.Calcd for C₂₁H₂₇ClN₂O: C, 70.28; H, 7.58; N, 7.81. Found: C, 70.32; H,7.76; N, 7.63.

EXAMPLE 12 Synthesis of1-(mesityl)-3-(2-hydroxy-3-tert-butyl-5-methylphenyl)-4,5-dihydro-imidazoliumchloride

N-(Mesityl)-N′-(2-hydroxy-3-tert-butyl-5-methylphenyl)-oxalamide (2.385g, 6.5 mmol, 1 eq), prepared according to the synthesis method describedin Example 7, was treated in a fashion similar to that described inExample 10 for N-(mesityl)-N′-(2-hydroxyphenyl)-oxalamide). Theresulting solid was washed with ether, to provide the desired product asa white powder (0.884 g, 2.28 mmol, 35% yield). ¹H NMR (300 MHz, CDCl₃)δ 8.42 (s, 1H), 7.10 (d, J=1.5 Hz, 1H), 6.96 (s, 2H), 6.80 (s, 1H), 4.79(t, J=11.1 Hz, 2H), 4.43 (t, J=9.6 Hz, 2H), 2.47 (s, 6H), 2.30 (s, 3H),2.27 (s, 3H), 1.41 (s, 9H); ¹³C NMR (75 MHz, CDCl₃) δ 158.7, 148.1,144.2, 140.7, 135.8, 130.8, 130.6, 130.3, 128.9, 127.5, 121.6, 52.3,51.6, 35.6, 30.1, 21.2, 21.1, 18.6. Anal. Calcd for C₂₃H₃₁ClN₂O: C,71.39; H, 8.07; N, 7.24. Found: C, 72.01; H, 8.03; N, 7.36.

EXAMPLE 13 Synthesis of1-(2,6-diisopropylphenyl)-3-(2-hydroxy-3-(adamant-1-yl)-5-methylphenyl)-4,5-dihydro-imidazoliumchloride

N-(2,6-Diisopropylphenyl)-N′-(2-hydroxy-3-(adamant-1-yl)-5-methylphenyl)-oxalamide(1.83 g, 3.7 mmol, 1 eq), prepared according to the synthesis methoddescribed in Example 9, was treated in a fashion similar to thatdescribed in Example 10 for N-(mesityl)-N′-(2-hydroxyphenyl)-oxalamide).The resulting solid was washed with ether, to provide the desiredproduct as a white powder (1.19 g, 2.3 mmol, 63% yield). ¹H NMR (300MHz, CDCl₃) δ 8.23 (s, 1H), 7.45 (t, J=8.1 Hz, 1H), 7.27 (d, J=8.1 2H),7.04 (s, 1H), 6.80 (s, 1H), 4.88 (t, J=10.8 Hz, 2H), 4.45 (t, J=11.7 Hz,2H), 3.41 (septet, J=6.6 Hz 2H), 2.28 (s, 3H), 2.13 (bs, 6H), 2.04 (bs,3H), 1.74 (m, 6H), 1.34 (d, J=6.9 Hz, 6H), 1.29 (d, J=6.6 Hz, 6H); ¹³CNMR (75 MHz, CDCl₃) δ 158.4, 148.3, 147.3, 144.4, 131.4, 130.8, 130.2,128.8, 127.8, 125.2, 121.1, 54.0, 52.4, 40.8, 37.8, 37.2, 29.2, 28.8,25.5, 24.4, 21.1. Anal. Calcd for C₃₂H₄₃ClN₂O: C, 75.78; H, 8.55; N,5.52. Found: C, 74.78; H, 8.64; N, 5.44.

EXAMPLE 14

1-(mesityl)-3-(2-hydroxyphenyl)-4,5-dihydro-imidazolium chloride andpotassium hexamethyl disilazane (2.1 equiv.) were dissolved in THF (20ml) at room temperature, giving a cloudy, light yellow solution. Thissolution was then stirred for minutes. A solution of (PdClMePEt₃)₂ (0.5equiv.) in THF was then added, producing a light yellow solution with aprecipitate. The solution was then stirred for one hour. The solutionwas then filtered through celite, and the THF was removed under reducedpressure until roughly 2 ml remained. Pentane (10 mL) was then added tothe solution which was then allowed to sit overnight at −40° C. The nextday, a white precipitate was observed to have developed. The product wasthen recovered via filtration.

EXAMPLE 15

1-(2,6-diisopropylphenyl)-3-(2-hydroxyphenyl)-4,5-dihydro-imidazoliumchloride and potassium hexamethyl disilazane (2.1 equiv.) were dissolvedin THF (20 ml) at room temperature, giving a cloudy, light yellowsolution. This solution was then stirred for 5 minutes. A solution of(PdClMePPh₃)₂ (0.5 equiv.) in THF was then added, producing a lightyellow solution with a precipitate. The solution was then stirred forone hour. The solution was then filtered through celite, and the THF wasremoved under reduced pressure until roughly 2 ml remained. Pentane (10mL) was then added to the solution which was then allowed to sitovernight at −40° C. The next day, a white precipitate was observed tohave developed. The product was then recovered via filtration.

EXAMPLE 16

1-(mesityl)-3-(2-hydroxy-3-tert-butyl-5-methylphenyl)-4,5-dihydro-imidazoliumchloride and potassium hexamethyl disilazane (2.1 equiv.) were dissolvedin THF (20 ml) at room temperature, giving a cloudy, light yellowsolution. This solution was then stirred for 5 minutes. A solution of(PdClMePPh₃)₂ (0.5 equiv.) in THF was then added, producing a lightyellow solution with a precipitate. The solution was then stirred forone hour. The solution was then filtered through celite, and the THF wasremoved under reduced pressure until roughly 2 ml remained. Pentane (10mL) was then added to the solution which was then allowed to sitovernight at −40° C. The next day, a white precipitate was observed tohave developed. The product was then recovered via filtration.

EXAMPLE 17

1-(2,6-diisopropylphenyl)-3-(2-hydroxy-3-adamantyl-5-methylphenyl)-4,5-dihydro-imidazoliumchloride and potassium hexamethyl disilazane (2.1 equiv.) were dissolvedin THF (20 ml) at room temperature, giving a cloudy, light yellowsolution. This solution was then stirred for 5 minutes. A solution of(PdClMePPh₃)₂ (0.5 equiv.) in THF was then added, producing a lightyellow solution with a precipitate. The solution was then stirred forone hour. The solution was then filtered through celite, and the THF wasremoved under reduced pressure until roughly 2 ml remained. Pentane (10mL) was then added to the solution which was then allowed to sitovernight at −40° C. The next day, a white precipitate was observed tohave developed. The product was then recovered via filtration.

EXAMPLE 18

1-(2,6-diisopropylphenyl)-3-(2-hydroxy-3-adamantyl-5-methylphenyl)-4,5-dihydro-imidazoliumchloride and potassium hexamethyl disilazane (2.1 equiv.) were dissolvedin THF (20 ml) at room temperature, giving a cloudy, light yellowsolution. This solution was then stirred for 5 minutes. A solution ofNiMesBr(PPh₃)₂ (1 equiv.) in THF was then added, producing a lightyellow solution with a precipitate. This solution was then stirred for 1hour. The solution was then filtered through celite, and the THF wasremoved under reduced pressure until roughly 2 ml remained. Pentane (10mL) was then added to the solution, which was then allowed to sitovernight at −40° C. The next day, a yellow precipitate had developed.The product was then recovered via filtration.

EXAMPLE 19

1-(2,6-diisopropylphenyl)-3-(2-hydroxyphenyl)-4,5-dihydro-imidazoliumchloride and potassium hexamethyl disilazane (2.1 equiv.) were dissolvedin THF (20 ml) at room temperature, giving a cloudy, light yellowsolution. This solution was then stirred for 5 minutes. A solution ofNiMesBr(PPh₃)₂ (1 equiv.) in THF was then added, producing a lightyellow solution with a precipitate. This solution was then stirred for 1hour. The solution was then filtered through celite, and the THF wasremoved under reduced pressure until roughly 2 ml remained. Pentane (10mL) was then added to the solution, which was then allowed to sitovernight at −40° C. The next day, a yellow precipitate had developed.The product was then recovered via filtration.

EXAMPLE 20

1-(2,6-diisopropylphenyl)-3-(2-hydroxy-3-adamantyl-5-methylphenyl)-4,5-dihydro-imidazoliumchloride and potassium hexamethyl disilazane (2.1 equiv.) were dissolvedin THF (20 ml) at room temperature, giving a cloudy, light yellowsolution. This solution was then stirred for 5 minutes. A solution ofTiCl₄(thf)₂ (0.5 equiv.) in THF was then added, producing a dark redsolution with precipitate. This solution was then stirred for 1 hour.The solution was then filtered through celite, and the THF was removedunder reduced pressure. The resulting solid was then taken up in diethylether and allowed to sit overnight at −40° C. The next day dark redcrystals were observed to have developed. The product was then recoveredvia filtration.

EXAMPLE 21

1-(2,6-diisopropylphenyl)-3-(2-hydroxy-3-adamantyl-5-methylphenyl)-4,5-dihydro-imidazoliumchloride and potassium hexamethyl disilazane (2.1 equiv.) were dissolvedin tetrahydrofuran (20 ml) at room temperature, giving a cloudy, lightyellow solution. This solution was then stirred for 5 minutes. Asolution of ZrCl₄ (0.5 equiv.) in THF was then added, producing a lightyellow solution with precipitate. This solution was then stirred for 1hour. The solution was then filtered through celite, and the THF wasremoved under reduced pressure. The resulting solid was then taken up indiethyl ether and was allowed to sit overnight at −40° C. The next day alight yellow precicpitate has developed. The product was then recoveredvia filtration.

EXAMPLE 22

In a dry box, to a clean, dry reactor cell of an Argonaut Endeavor®containing a disposable glass reaction insert was added 0.438 g (7.50mmol) solid MAO. The reactor cell was sealed and pressure tested to 400psig. To the reactor cell was then added 5.0 mL of toluene. Stirring wascommenced and the reactor was heated to 65° C. and pressurized withethylene gas to 400 psig. Upon equilibration of the reactor temperatureand pressure, 5.1 mg (5 μmol)bis(1-2,6-diisopropylphenyl)-3-(2-hydroxy-3-adamantyl-5-methylphenyl)-4,5-dihydro-imidazolyl)titanium dichloride dissolved in 0.5 mL toluene was then added to thereactor cell via an addition port. The addition port was thenimmediately rinsed with an additional 0.5 mL of toluene and the reactiontimer was engaged. The reaction was then allowed to proceed for 90minutes with a continuous ethylene feed. After 90 minutes, the reactionwas terminated by venting the excess ethylene gas. The reactor cell wasthen opened and the glass cell liner and its contents were removed. Theglass cell liner and contents were then removed from the dry box and 2–3mL of acidified MeOH (10 wt % HCl) was slowly and carefully added to thecontents of the glass cell liner. After standing for several minutes,the contents of the glass cell liner were dumped into 200 mL rapidlystirred MeOH, where they were kept for one to two hours. The resultingmixture was then washed with excess MeOH and filtered to dryness.Residual solvents were removed by heating the resultant white powder at60° C. under vacuum for 18 hours to yield 1.84 g of polymer product.

EXAMPLE 23

In a dry box, to a clean, dry reactor cell of an Argonaut Endeavors®containing a disposable glass reaction insert was added 0.292 g (5.00mmol) solid MAO. The reactor cell was then sealed and pressure tested to400 psig. To the reactor cell was then added 5.0 mL of toluene. Stirringwas commenced and the reactor cell was heated to 65° C. and pressurizedwith ethylene gas to 400 psig. Upon equilibration of the reactortemperature and pressure, 5.4 mg (5 μmol)bis(1-(2,6-diisopropylphenyl)-3-(2-hydroxy-3-adamantyl-5-methylphenyl)-4,5-dihydro-imidazolyl)zirconium dichloride dissolved in 0.5 mL toluene was added to thereactor cell via an addition port. The addition port was thenimmediately rinsed with an additional 0.5 mL of toluene and the reactiontimer was engaged. The reaction was then allowed to proceed for 90minutes with continuous ethylene feed. After 90 minutes, the reactionwas terminated by venting the excess ethylene gas. The reactor cell wasthen opened and the glass cell liner and its contents were removed. Theglass cell liner and contents were then removed from the dry box and 2–3mL of acidified MeOH (10 wt % HCl) was slowly and carefully added to thecontents of the glass cell liner. After standing for several minutes,the contents of the glass cell liner were dumped into 200 mL of rapidlystirred MeOH, where they were kept for one to two hours. The resultingmixture was then washed with excess MeOH and filtered to dryness.Residual solvents were removed by heating the resultant white powder at60° C. under vacuum for 18 hours to yield 1.35 g of polymer product.

EXAMPLE 24

In a dry box, to a clean, dry reactor cell of an Argonaut Endeavor®containing a disposable glass reaction insert was added 0.438 g (7.50mmol) solid MAO. The reactor cell was then sealed and pressure tested to400 psig. To the reactor cell was then added 5.0 mL of toluene. Stirringwas then commenced and the reactor cell was heated to 65° C. andpressurized with ethylene gas to 400 psig. Upon equilibration of thereactor temperature and pressure, 4.6 mg (5 μmol)1-(2,6-diisopropylphenyl)-3-(2-hydroxy-3-adamantyl-5-methylphenyl)-4,5-dihydroimidazolylmethyl triphenylphosphine nickel dissolved in 0.5 mL of toluene wasadded to the reactor cell via an addition port. The addition port wasthen immediately rinsed with an additional 0.5 mL toluene and thereaction timer was engaged. The reaction was then allowed to proceed for90 minutes with continuous ethylene feed. After 90 minutes, the reactionwas terminated by venting the excess ethylene gas. The reactor cell wasthen opened and the glass cell liner and its contents were removed. Theglass cell liner and contents were then removed from the dry box and 2–3mL of acidified MeOH (10 wt % HCl) was slowly and carefully added to thecontents of the glass cell liner. After standing for several minutes,the contents of the glass cell liner were dumped into 200 mL rapidlystirred MeOH, where they were kept for one to two hours. The resultingmixture was then washed with excess MeOH and filtered to dryness.Residual solvents were removed by heating the resultant white powder at60° C. under vacuum for 18 hours to yield 0.35 g of polymer product.

EXAMPLE 25

In a dry box, to a clean, dry reactor cell of an Argonaut Endeavor®containing a disposable glass reaction insert was added 0.292 g (5.00mmol) solid MAO. The reactor cell was then sealed and pressure tested to400 psig. To the reactor cell was then added 1.0 mL of anorbornene/toluene solution (79 wt % norbornene in toluene) followed by4.0 mL of toluene. Stirring was then commenced and the reactor cell washeated to 65° C. and pressurized with ethylene gas to 400 psig. Uponequilibration of the reactor temperature and pressure, 5.1 mg (5 μmol)bis(1-2,6-diisopropylphenyl)-3-(2-hydroxy-3-adamantyl-5-methylphenyl)-4,5-dihydro-imidazolyl)titanium dichloride dissolved in 0.5 mL of toluene was added to thereactor cell via an addition port. The addition port was thenimmediately rinsed with an additional 0.5 mL of toluene and the reactiontimer was engaged. The reaction was then allowed to proceed for 120minutes with continuous ethylene feed. After 90 minutes, the reactionwas terminated by venting the excess ethylene gas. The reactor cell wasopened and the glass cell liner and its contents were removed. The glasscell liner and contents were then removed from the dry box and 2–3 mL ofacidified MeOH (10 wt % HCl) was slowly and carefully added to thecontents of the glass cell liner. After standing for several minutes,the contents of the glass cell liner were dumped into 200 mL rapidlystirred MeOH, where they were kept for one to two hours. The resultingmixture was then washed with excess MeOH and filtered to dryness.Residual solvents were removed by heating the resultant white powder at60° C. under vacuum for 18 hours to yield 2.69 g of polymer product.

EXAMPLE 26

In a dry box, to a clean, dry reactor cell of an Argonaut Endeavor®containing a disposable glass reaction insert was added 0.292 g (5.00mmol) solid MAO. The reactor cell was then sealed and pressure tested to400 psig. To the reactor cell was then added 1.0 mL of anorbornene/toluene solution (79 wt % norbornene in toluene) followed by4.0 mL of toluene. Stirring was then commenced and the reactor washeated to 65° C. and pressurized with ethylene gas to 400 psig. Uponequilibration of the reactor temperature and pressure, 5.4 mg (5 mmol)bis(1-(2,6-diisopropylphenyl)-3-(2-hydroxy-3-adamantyl-5-methylphenyl)-4,5-dihydro-imidazolyl)zirconium dichloride dissolved in 0.5 mL toluene was added to thereactor cell via an addition port. The addition port was thenimmediately rinsed with an additional 0.5 mL of toluene and the reactiontimer was engaged. The reaction was then allowed to proceed for 120minutes with continuous ethylene feed. After 90 minutes, the reactionwas terminated by venting the excess ethylene gas. The reactor cell wasthen opened and the glass cell liner and its contents were removed. Theglass cell liner and contents were then removed from the dry box and 2–3mL of acidified MeOH (10 wt % HCl) was slowly and carefully added to thecontents of the glass cell liner. After standing for several minutes,the contents of the glass cell liner were dumped into 200 mL rapidlystirred MeOH, where they were kept for one to two hours. The resultingmixture was then washed with excess MeOH and filtered to dryness.Residual solvents were then removed by heating the resultant whitepowder at 60° C. under vacuum for 18 hours to yield 1.30 g of polymerproduct.

EXAMPLE 27

In a dry box, to a clean, dry reactor cell of an Argonaut Endeavor®containing a disposable glass reaction insert was added 0.292 g (5.00mmol) solid MAO. The reactor cell was sealed and pressure tested to 400psig. To the reactor cell was then added 1.0 mL of a norbornene/toluenesolution (79 wt % norbornene in toluene) followed by 4.0 mL of toluene.Stirring was then commenced and the reactor was heated to 65° C. andpressurized with ethylene gas to 400 psig. Upon equilibration of thereactor temperature and pressure, 6.8 mg (7.5 μmol)1-(2,6-diisopropylphenyl)-3-(2-hydroxy-3-adamantyl-5-methylphenyl)-4,5-dihydroimidazolylmethyl triphenylphosphine nickel dissolved in 0.5 mL toluene was thenadded to the reactor cell via an addition port. The addition port wasthen immediately rinsed with an additional 0.5 mL of toluene and thereaction timer was engaged. The reaction was then allowed to proceed for120 minutes with continuous ethylene feed. After 90 minutes, thereaction was terminated by venting the excess ethylene gas. The reactorwas then opened and the glass cell liner and its contents were removed.The glass cell liner and contents were then removed from the dry box and2–3 mL of acidified MeOH (10 wt % HCl) was slowly and carefully added tothe contents of the glass cell liner. After standing for severalminutes, the contents of the glass cell liner were dumped into 200 mLrapidly stirred MeOH, where they were kept for one to two hours. Theresulting mixture was then washed with excess MeOH and filtered todryness. Residual solvents were then removed by heating the resultantwhite powder at 60° C. under vacuum for 18 hours to yield 0.15 g ofpolymer product.

1. A polymerization catalyst comprising: a metal center selected from Ti Zr and Hf with at least one chelating ligand comprising a carbene with an anionic moiety, wherein the at least one chelating ligand has a structure selected from

wherein R is any hydrocarbyl group; each R₁ is independently any hydrocarbyl group; R² is any hydrocarbyl group; n is selected from 1 and 2; and X is selected from O, N and S; and wherein both the carbene and the anionic moiety are coordinated to the metal center.
 2. The polymerization catalyst of claim 1, wherein the polymerization catalyst comprises two chelating ligands.
 3. The polymerization catalyst of claim 2, further comprising two halide ligands, wherein the halide ligands are each independently selected from Cl, Br and I.
 4. A process for preparing a homopolymer or copolymer comprising contacting at least one α-olefin monomer with the polymerization catalyst of claim 2 in the presence of an aluminum activator.
 5. A process for preparing a copolymer comprising contacting the polymerization catalyst of claim 2 with at least two different monomers selected from α-olefins, norbornene, norbornene containing a pendent hydrocarbyl substituent and styrene in the presence of an aluminum activator.
 6. A process for preparing a homopolymer or copolymer comprising: providing a polymerization catalyst comprising a metal center selected from Ti, Zr, Hf, Ni and Pd with at least one chelating ligand comprising a carbene with an anionic moiety, wherein the at least one chelating ligand has a structure selected from

wherein R is any hydrocarbyl group; each R¹ is independently any hydrocarbyl group; R² is any hydrocarbyl group; n is selected from 1 and 2; and X is selected from O, N and S; wherein both the carbene and the anionic moiety are coordinated to the metal center; and with the proviso that when the metal center is Ni or Pd the polymerization catalyst comprises one of the at least one chelating ligand; providing ethylene; and, contacting the ethylene with the polymerization catalyst.
 7. The process of claim 6, further comprising: providing at least one monomer selected from α-olefins, norbornenes and styrene; providing an aluminum activator; and, contacting the ethylene and the polymerization catalyst with the at least one monomer selected from α-olefins, norbornenes and styrene in the presence of the aluminum activator.
 8. The process of claim 6, wherein the polymerization catalyst further comprises a hydrocarbyl ligand and a neutral ligand coordinated with the metal center; wherein the hydrocarbyl ligand is selected from Me, Ph and Mesityl and the neutral ligand is selected from phosphine, amine and pyridine.
 9. The process of claim 6, wherein the polymerization catalyst further comprises a chelating hydrocarbyl ligand coordinated with the metal center. 